PRECURSOR AND METHOD FOR PREPARING Ni BASED CATHODE MATERIAL FOR RECHARGEABLE LITHIUM ION BATTERIES

ABSTRACT

A crystalline precursor compound for manufacturing a lithium transition metal based oxide powder usable as an active positive electrode material in lithium-ion batteries, the precursor having a general formula Li 1-a ((Ni z (Ni 0.5 Mn 0.5 ) y Co x ) 1-k A k ) 1+a O 2 , wherein A comprises at least one element of the group consisting of: Mg, Al, Ca, Si, B, W, Zr, Ti, Nb, Ba, and Sr, with 0.05≤x≤0.40, 0.25≤z≤0.85, x+y+z=1, 0≤k≤0.10, and 0≤a≤0.053, wherein said crystalline precursor powder has a crystalline size L, expressed in nm, with 15≤L≤36.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.16/562,694, filed Sep. 6, 2019, which is a continuation in part of U.S.patent application Ser. No. 16/487,525, filed Aug. 21, 2019, which is anational stage application of International Patent Application No.PCT/EP2018/053638, filed on Feb. 14, 2018, which claims the benefit ofEuropean Patent Application No. 17159083.9, filed on Mar. 3, 2017.

TECHNICAL FIELD AND BACKGROUND

This invention relates to a crystalline precursor of and a method toprepare a Ni-excess “NMC” cathode powdery material on a large-scale andat low cost. By “NMC” we refer to lithium-nickel-manganese-cobalt-oxide.The Ni-excess NMC powder can be used as a cathode active material inlithium-ion rechargeable batteries. Batteries containing the cathodematerials of the invention enhance their performances, such as providinga higher cycle stability and a low content of soluble base.

The global market of lithium-ion batteries (LIBs) has been concentratingon large batteries. The term “large batteries” refers to applications inelectric vehicles (EV), as well as in stationary power stations. TheseEV or large stationaries require much larger power sources than thepreviously dominating batteries for portable devices such as laptops,smartphones, tablets, etc. Therefore, there are fundamentally differentrequirements for the “large battery” cathode materials, not onlyperformance-wise, but also from the point of view of resource scarcity.Previously, LiCoO₂ (LCO) was used as the cathode material for mostrechargeable lithium batteries. However, LCO is not sustainable for thelarge batteries due to the limited cobalt resources—as approximately 30%of the cobalt production worldwide is currently already used forbatteries, according to the Cobalt Development Institute. Therefore,lithium-nickel-cobalt-manganese-based oxide (NMC), having roughly thestoichiometry LiM′O₂, where M′=Ni_(x′)Mn_(y′)Co_(z′) (when not doped)has become a promising alternative cathode material due to its lesscritical resources situation. This material has excellent cyclingproperties, long-life stability, high energy density, good structuralstability, and low cost. Various compositions of NMC have been developedto improve the energy density of NMC by relatively increasing the amountof Ni, without losing its advantages mentioned before. Typical NMC basedmaterials are “111”, “442”, “532”, and “622”: “111” withM′=Ni_(1/3)Mn_(1/3)Co_(1/3), “442” with M′=Ni_(0.4)Mn_(0.4)Co_(0.2),“532” with M′=Ni_(0.5)Mn_(0.3)Co_(0.2), “622” withM′=Ni_(0.6)Mn_(0.2)Co_(0.2). The NMC cathode materials contain lesscobalt because it is replaced by nickel and manganese. Since nickel andmanganese are cheaper than cobalt and relatively more abundant, NMCpotentially replaces LiCoO₂ in the large batteries.

NMC cathode materials can roughly be understood as a solid statesolution of LiCoO₂, LiNi_(0.5)Mn_(0.5)O₂ and LiNiO₂, corresponding tothe general formula Li_(1-a)[Ni_(z)(Ni_(0.5)Mn_(0.5))_(y)Co_(x)]_(1+a)O₂, where “z” stands for the Ni(3+)-excess, as in LiNi_(0.5)Mn_(0.5)O₂Ni is divalent and in LiNiO₂ Ni is trivalent. At 4.3V, the nominalcapacity of LiCoO₂ and LiNi_(0.5)Mn_(0.5)O₂ is about 160mAh/g, against220 mAh/g for LiNiO₂. The reversible capacity of any NMC compound can beroughly estimated from these capacities. For example, NMC 622 can beunderstood as 0.2 LiCoO₂+0.4 LiNi_(0.5)Mn_(0.5)O₂+0.4 LiNiO₂. Thus, theexpected capacity equals 0.2×160+0.4×160+0.4×220=184 mAh/g. The capacityincreases with “Ni-excess”, where “Ni-excess” is the fraction of3-valent Ni; for example, in NMC 622, the Ni-excess is 0.4 (if we assumelithium stoichiometry with a Li/(Ni+Mn+Co) atomic ratio of 1.0).Obviously, the capacity increases with the Ni-excess, so that at thesame voltage, Ni-excess NMC possesses a higher energy density than LCO,which means less weight or volume of cathode material is required for acertain energy demand when using Ni-excess NMC instead of LCO.Additionally, due to the lower price of nickel and manganese compared tocobalt, the cost of cathode per unit of delivered energy is muchreduced. Thus, the higher energy density and lower cost of Ni-excessNMC—by contrast to LCO—is more preferred in the “large battery” market.

There are two major trends to achieve a high energy density. One trendis to increase the Ni-excess up to very high values. InNCA—LiNi_(0.8)Co_(0.15)Al_(0.05)O₂, for example, the Ni-excess is veryhigh; it is 0.8 as all Ni is 3 valent. In NC91—LiNi_(0.9)Co_(0.1)O₂ theNi-excess is even 0.9. These cathodes have very high capacities even atrelatively low charge voltage. As an example, NC91 has capacities ashigh as 220mAh/g at 4.3V. These cathodes have a major disadvantage: ifthe battery is fully charged and the cathodes are in the delithiatedstate, the values of “x” in the resulting Li_(1-x)MO₂ are high. Thesehighly delithiated cathodes are very unsafe when in contact withelectrolyte. Once a certain temperature in the battery has been reached,the cathodes decompose and deliver oxygen which combusts theelectrolyte. Basically, the electrolytes reduce the cathode. After thereaction—as there is large Ni-excess—most of the transition metal is 2valent. Schematically—each mol of cathode can deliver one mol oxygen tocombust the electrolyte: NiO₂+electrolyte→NiO+{H₂O, CO₂}. The safetyissue of batteries is mostly caused by the combustion heat of theelectrolyte.

The other trend to achieve a high energy density is to increase theNi-excess towards intermediate values. Typical values for the Ni-excessrange from about 0.25 to about 0.6. This region we will refer as “highNi-excess”. The current invention refers to a process to prepare NMCwith high Ni-excess. The capacity at 4.2V or 4.3V of high Ni-excess NMCis less than that of “very high” Ni-excess compound (with Ni-excess ofsuperior to 0.6). However, the capacity can also be increased byincreasing the charge voltage. The resulting delithiated cathodes aresafer than the delithiated very high Ni-excess cathodes mentioned above.Whereas Ni tends to form NiO, Ni-M′ tends to form stable M′₃O₄compounds. These compounds have a higher final oxygen stoichiometry thusless oxygen is available to combust the electrolyte. As a result, thesafety of high Ni-excess cathodes is improved even if a higher chargevoltage is applied.

The prior art teaches that the cycle stability of NMC at high voltagemay be insufficient, however, it can be improved by applying a surfacecoating, as disclosed e.g. in WO2016-116862. The surface coatingbasically stabilizes the surface against unwanted side reactions betweenelectrolyte and cathode during cycling.

As the capacity of NMC material increases with Ni-excess, “Ni-excess”NMC cathode materials, like NMC 532 and NMC 622, possess a highercapacity in batteries than with less Ni, as for example NMC 111 (havinga Ni-excess of 0). However, the production becomes more and moredifficult with increasing Ni content. As an example—very high Ni-excesscathode materials like NCA cannot be prepared in air or using Li₂CO₃ asa lithium source. Because of the low thermodynamic stability of Li inNi-excess material, “soluble bases” occur easily on the surface of thefinal product, the concept of “soluble base” being explicitly discussedin e.g. WO2012-107313: the soluble base refers to surface impuritieslike lithium carbonate (Li₂CO₃) and lithium hydroxide (LiOH). Thesesoluble bases are a concern since especially residual Li₂CO₃ causes poorcycling stability in the lithium ion battery. Therefore, the preparationof very high Ni-excess cathode materials is performed in CO₂ freeoxidizing gas (typically oxygen) to reduce the soluble base content atincreasing temperature, and LiOH is used as a lithium source instead ofLi₂CO₃. Contrary to this, the low Ni NMC 111 can easily be prepared innormal air and using a low-cost Li₂CO₃ precursor.

The preparation of NMC 532 (having a Ni-excess of 0.2) is more difficultthan NMC 111, but NMC 532 can still be processed at large-scale througha low cost and simple solid state reaction under air. Thisprocess—referred to as “direct sintering”—is the firing of a blend of amixed metal precursor (for example M′(OH)₂ precursor) and a lithiumsource. The lithium source is preferably Li₂CO₃, as in the production ofNMC 111, due to its low price.

Another promising Ni-excess compound is NMC 622, whose Ni-excess is 0.4and its capacity is higher than that of NMC 532. However, compared toNMC 532 and NMC 111, it is very difficult to prepare NMC 622 with lowsoluble base using a large-scale and low cost process such as directsintering. As discussed in U.S. Pat. No. 7,648,693, these bases may comefrom unreacted Li₂CO₃ present in the reagents of the lithium sources,usually Li₂CO₃ or LiOH.H₂O, where LiOH.H₂O normally contains 1 wt %Li₂CO₃ impurity. These bases can also originate from the mixedtransition metal hydroxides that are used as the transition metal sourcein the production. The mixed transition metal hydroxide is usuallyobtained by co-precipitation of transition metal sulfates and anindustrial grade base such as NaOH. Thus, the hydroxide can contain aCO₃ ²⁻ impurity. During sintering with a lithium source the CO₃ ²⁻residual reacts with lithium and creates Li₂CO₃. As during sinteringLiM′O₂ crystallites grow, the Li₂CO₃ base will be accumulated on thesurface of these crystallites. Thus, after sintering at high temperaturein a high Ni-excess NMC, like NMC 622, carbonate compounds remain on thesurface of the final product. This base can dissolve in water, andtherefore the soluble base content can be measured by a technique calledpH titration, as discussed in U.S. Pat. No. 7,648,693.

The presence of soluble base in the final NMC material causes a seriousgas generation in full cells, which is usually called “bulging”. Thismay result in a poor cycle life of the battery, together with safetyconcerns. Therefore, in order to use Ni-excess NMC materials for largebattery applications, an effective and low cost processing method isnecessary that avoids the formation of such high soluble base contents.

The direct sintering method mentioned before is performed in trays in acontinuous manner. “Trays” are ceramic vessels which contain the blendor product during sintering, they are sometimes also referred to as“saggers”. The trays are continuously fed to a furnace, and during themovement through the conveyor furnace the reaction towards the finalsintered LiM′O₂ proceeds. The sintering cost depends strongly on thethroughput of the sintering process. The faster the trays move acrossthe furnace (referred to as the “sintering time”) and the more blend thetrays carry (referred to as the “tray load”), the higher the throughputof the furnace is. Moreover, the furnace has a high investment cost.Therefore, if the throughput is small, the furnace depreciation andoperating cost significantly contributes to the total process cost. Inorder to reduce manufacturing cost, a high throughput is thus desired.

Many large-scale direct sintering production methods for Ni-excess NMChave been tried. As the Ni-excess increases, the direct sinteringbecomes more difficult. It is observed that high Ni-excess NMC requireslong sintering times and a low tray load to be successful. Since highNi-excess NMC has a too low “tray throughput”, the direct sinteringproduction is not available to produce a high quality material at anacceptable low cost. For example, when using a Li₂CO₃ precursor, thethroughput limitation can be traced back to the relatively highthermodynamic stability of Li₂CO₃ causing slower reaction kinetics whenthe reaction proceeds. The mechanism that slows down the reaction speedis a gas phase limitation, since due to a low CO₂ equilibrium partialpressure, the removal of CO₂ hinders the reaction. Therefore, theapplication of other lithium sources having a lower thermodynamicstability could solve this issue. LiOH.H₂O is such a precursor and thecorresponding H₂O equilibrium partial pressures are higher than those ofCO₂. Thus, LiOH.H₂O is widely applied as a precursor for directsintering higher Ni containing cathode materials. This typical processto prepare high Ni-excess NMC is for example applied in US2015/0010824.LiOH.H₂O with a low Li₂CO₃ impurity as a lithium source is blended withthe mixed transition metal hydroxide at the target composition, andsintered at high temperature under an air atmosphere. In this process,the base content of such high Ni-excess NMC final product (like NMC 622)is much reduced.

However, LiOH.H₂O makes excess vapor during heating and sintering steps,resulting in various problems. For example, LiOH.H₂O has a low meltingpoint of about 400° C. At that temperature the reactivity of a metalprecursor (like M′OOH) with LiOH.H₂O is not high. As a result moltenLiOH.H₂O is present at the same time as large amounts of H₂O vapor arecreated. These vapor streams physically cause a de-mixing of the blend,resulting in a final product having an inhomogeneous chemicalcomposition, where especially the Li/M′ atomic ratio will vary within atray. The larger the tray load is, the more severe this issue becomes.Additionally, there is also a heat limitation issue. If the tray load ishigh then the blend in the center of the trays will be less sintered.Thus—at high tray throughput—inhomogeneously sintered product will beachieved. The larger the tray load is, the more severe these issuesbecome.

For a high quality final cathode material powder with a homogeneouscomposition, the variation of Li/M′ atomic ratio and sintering degree ofparticles within the powder needs to be limited. Therefore, in order toachieve a high quality product a low tray load is required. If wecompare the direct firing using Li₂CO₃ precursor and LiOH.H₂O precursor,then the LiOH.H₂O allows a higher tray throughput, but in an economical,mass production process the tray throughput must still be higher. Thetray based conveyor furnace consists of a continuous firing kiln with amotor driven roller way, which is good for consistent high-volumeproduction of NMC. However, generally there is a heat transferlimitation of the blend in the trays because both tray and product aregood heat insulators, resulting in an inhomogeneous state of sinteringin the final product. Furthermore, this heat transfer issue will be moresevere if the firing time is reduced in order to increase throughput.Therefore, improved sintering methods to enhance the transport of heatwithin the blend are necessary for a large-scale preparation of highquality NMC.

Rotary furnace technology provides a faster transport of heat within theblend. It also prevents de-mixing of the blend. A typically usedindirect-fired sintering rotary furnace is basically a metallic rotatingtube which is heated from the outside, such as disclosed in U.S. Pat.No. 7,939,202. Cold blend or product is transported towards the hot zoneof the tube, and within the tube the blend or product continuouslymoves, and is continuously heated, thereby preventing a de-mixing whichprevents an inhomogeneous Li/M′ atomic ratio. Thus, a rotary furnace hasmuch less heat transfer limitations, and provides a much higherthroughput and has a low operating cost per production capacity for anintrinsically lower investment cost. Rotary furnaces are also verycompact and allow to increase production capacity without need to usemore land. However, as said before, direct sintering requires relativelylong sintering times and a relatively high temperature, (for exampleexceeding 800° C. for NMC 622) to obtain a high quality product. It isdifficult to obtain a long sintering time in a rotary furnace. Also, atthe high sintering temperature the lithium in a lithiated transitionmetal oxide will react with the tube material and cause tube corrosion.Therefore, indirect-fired sintering rotary furnaces are not suitable fordirect sintering.

Besides, direct sintering also split firing has been proposed. U.S. Pat.No. 7,648,693 proposes a split method, where the firing is conducted intwo steps: a first lithiation at relatively low temperature, like 700°C., and a second step of sintering at a higher temperature. In thispatent, a large-scale preparation of LiM′O₂ withM′=Ni_(0.27)(Mn_(0.50)Ni_(0.50))_(0.53)Co_(0.2) is achieved with a finalproduct that is almost free of soluble base, resulting in improvedcycling stability. The split method could thus be a potential way toprepare e.g. NMC 622 free of soluble base and at a low cost. In thesplit method, all lithium is added to the blend before the 1^(st)sintering. Under such conditions, it is practically impossible to fullyreact the metal precursor with the Li₂CO₃ at reasonable high throughput.Therefore, the split method is not usable for the large-scale productionof NMC 622 with Li₂CO₃ as a lithium source because excessive amounts ofpreheated air have to be pumped through the reactor. Practically, thesplit method is limited to lower Ni-excess NMC, such as NMC 532.

A further variation of the split method is suggested in U.S. Pat. No.9,327,996B2. The method for producing NMC—as is disclosed in U.S. Pat.No. 9,327,996B2—provides a step of firing a lithium-containing carbonateblend in a rotary furnace to produce a lithiated intermediate product.Rotary firing gives a large benefit for the 1^(st) sintering. It allowsfor lower cost and excellent production efficiency. However, in case ofhigh Ni-excess NMC, the preparation of a fully lithiated intermediateproduct is not possible because it is impossible to finish thelithiation reaction when using Li₂CO₃ as a lithium source. Thus, theresidual Li₂CO₃ content after the 1^(st) sintering is too high. During a2^(nd) sintering at high throughput, it will be practically impossibleto remove sufficient Li₂CO₃ thus the soluble base content of the finalproduct will be too high. The final product will have a poor performancedue to high bulging and poor cycling stability.

Therefore, the object of the present invention is to provide a low costand efficient manufacturing process making use of an inventiveintermediate product, to supply lithium transition metal oxide cathodematerials having a Ni-excess, and especially suitable for higher voltagebattery applications, where the charge voltage is at least 4.3V.

SUMMARY

Viewed from a first aspect, the invention can provide a crystallineprecursor compound or intermediate product for manufacturing a lithiumtransition metal based oxide powder usable as an active positiveelectrode material in lithium-ion batteries, the precursor having ageneral formulaLi_(1-a)((Ni_(z)(Ni_(0.5)Mn_(0.5))_(y)Co_(x))_(1-k)A_(k))_(1+a)O₂,wherein A comprises at least one element of the group consisting of: Mg,Al, Ca, Si, B, W, Zr, Ti, Nb, Ba, and Sr, with 0.05≤x≤0.40, 0.25≤z≤0.85,x+y+z=1, 0≤k≤0.10, and 0≤a≤0.053, wherein said crystalline precursorpowder has a crystalline size L, expressed in nm, with 15≤L≤36. Thecrystalline precursor may have a Li₂CO₃ content of at most 0.4 wt %. Inan embodiment, 0.35≤z≤0.50. In another embodiment, 0.03≤a≤0.053. In anadditional embodiment, 0.15≤x≤0.20. The crystalline precursor compoundof the previous embodiments may have an integrated intensity ratioI003/I104<1, wherein I003 and I104 are the peak intensities of the Braggpeaks (003) and (104) of the XRD pattern of the crystalline precursorcompound. Also, the precursor compound may have an integrated intensityratio I003/I104<0.9. In another embodiment, the precursor compound mayhave a ratio R of the intensities of the combined Bragg peak (006, 102)and the Bragg peak (101) with R=((I006+I102)/I101) and 0.5<R<1.16. Inall of these embodiments, the precursor may also have a crystalline sizeL expressed in nm, with 25≤L≤36.

Viewed from a second aspect, the invention can provide a method forpreparing a positive electrode material having the general formulaLi_(1-a′)M′_(1+a′)O₂, with M′=(Ni_(z)(Ni_(0.5)Mn_(0.5))_(y)Co_(x))_(1-k)A_(k), wherein x+y+z=1, 0.05≤x≤0.40, 0.25≤z≤0.85, A is a dopant,0≤k≤0.1, and

-   -   0.10≤a′≤0, the method comprising the steps of:    -   providing a M′-based precursor prepared from the        co-precipitation of metal salts with a base;    -   mixing the M′-based precursor with either one of LiOH, Li₂O and        LiOH.H₂O, thereby obtaining a first mixture, whereby the Li to        transition metal ratio in the first mixture is between 0.9 and        1.0,    -   sintering the first mixture in an oxidizing atmosphere in a        rotary kiln at a temperature between 650 and 850° C., for a time        between ⅓ and 3 hours, thereby obtaining the crystalline        precursor powder (or intermediate product) of the first aspect        of the invention,    -   optionally, mixing the crystalline precursor powder with either        one of LiOH, Li₂O and LiOH.H₂O, thereby obtaining a second        mixture, and    -   sintering the second mixture or the crystalline precursor in an        oxidizing atmosphere at a temperature between 800 and 1000° C.,        for a time between 6 and 36 hours, whereby the positive        electrode material having the general formula        Li_(1-a′)M′_(1+a′)O₂ as defined above is obtained. In a        particular method embodiment, a method is provided for preparing        a positive electrode material comprising a core material having        the general formula Li_(1-a′)M′_(1+a′)O₂, with        M′=(Ni_(z)(Ni_(0.5)Mn_(0.5))_(y)Co_(x))_(1-k)A_(k), wherein        x+y+z=1, 0.05≤x≤0.40, 0.25≤z≤0.85, A is a dopant, 0≤k≤0.1, and        −0.10≤a′≤0, and a coating comprising a metal M″-oxide, the        method comprising the steps of the method mentioned before for        providing the core material, and additionally the steps of        either:

A1) providing a third mixture comprising the core material beingobtained by the method mentioned before and a compound comprising M″,and

A2) heating the third mixture to a sintering temperature between 600° C.and 800° C.; or

B1) providing a fourth mixture comprising the core material beingobtained by the method mentioned before, a fluorine-containing polymerand a compound comprising M″, and

B2) heating the fourth mixture to a sintering temperature between 250and 500° C., or

C1) providing a fifth mixture comprising the core material obtained bythe method mentioned before, an inorganic oxidizing chemical compound,and a chemical that is a Li-acceptor, and

C2) heating the fifth mixture at a temperature between 300 and 800° C.in an oxygen comprising atmosphere. In this step the heating temperaturemay be limited to 350 to 450° C.

In this particular method the compound comprising M″ in either one ofsteps A1) and B1) may be either one or more of an oxide, a sulfate, ahydroxide and a carbonate, and M″ may be either one or more of theelements Al, Ca, Ti, Mg, W, Zr, B, Nb, and Si. In particular, it may beAl₂(SO₄)₃. Also in this method, the compound comprising M″ in either oneof steps A1) and B1) may be a nanometric alumina powder having a D50 ofinferior to 100 nm and a surface area of at least 50 m²/g. Also, thefluorine-containing polymer provided in step B1) may be either one of aPVDF homopolymer, a PVDF copolymer, a PVDF-HFP polymer (hexa-fluoropropylene) and a PTFE polymer, and wherein the amount offluorine-containing polymer in the fourth mixture is between 0.1 wt %and 2.0 wt %. In this method also, in step C1) the inorganic oxidizingchemical compound may be NaHSO₅, or either one of a chloride, achlorate, a perchlorate and a hypochloride of either one of potassium,sodium, lithium, magnesium and calcium, and the Li-acceptor chemical maybe either one of AlPO₄, Li₃AlF₆ and AlF₃. More preferably, both theinorganic oxidizing chemical compound and the Li-acceptor chemical maybe the same compound, being either one of Li₂S₂O₈, H₂S₂O₈ and Na₂S₂O₈.In this method also, in step C1) a nanosized Al₂O₃ powder may beprovided as a further Li-acceptor chemical.

In an embodiment of the different methods, in the rotary kiln an airflow is applied between 0.5 m³/kg and 3.5 m³/kg, and preferably between1.0 m³/kg and 2.5 m³/kg. In another embodiment of the different methods,the step of sintering the second mixture may be performed in a trayconveyor furnace wherein each tray carries at least 5 kg of mixture.Also, it may be preferred that between the step of providing a M′-basedprecursor and the step of mixing the M′-based precursor with either oneof LiOH, Li₂O and LiOH.H₂O the M′-based precursor is subjected to aroasting step at a temperature above 200° C. in a protective atmosphere,such as under N₂. In some embodiments, after this roasting step thetransition metals in the M′-based precursor have a mean oxidation stateof superior to 2.5 and a content of H₂O of inferior to 15 wt %. Also,after this roasting step the transition metals in the M′-based precursormay have a mean oxidation state of superior to 2.7 and a content of H₂Oof inferior to 5 wt %.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 : Process flow chart of Manufacturing Example 3

FIG. 2 : Lithium carbonate content of NMC samples prepared using directand double sintering

FIG. 3 : XRD patterns of the pretreated transition metal samples

FIG. 4 : XRD patterns of the intermediate and final product of NMCsamples prepared using double sintering

FIG. 5 : XRD patterns of the intermediate and final product of NMCsamples prepared using roasted transition metal source and doublesintering

FIG. 6 : XRD patterns of intermediate product with low Li/M′ atomicratio of NMC samples

FIG. 7 : Coin cell profile of NMC samples prepared using theintermediate product with low Li/M′ atomic ratio

FIG. 8 : Coin cell profile of Al and Al/F coated NMC samples

FIG. 9 : Coin cell profile of Al and Al/F coated NMC samples preparedusing roasted transition metal source

FIG. 10 : Total base content of NMC samples prepared using various airflow conditions during the 1^(st) sintering

FIG. 11 : Li/M′ atomic ratio of NMC samples prepared using various airflow conditions during the 1^(st) sintering

DETAILED DESCRIPTION

The current patent discloses an improved split firing method where the1^(st) sintering is done using a rotary furnace resulting in acrystalline precursor (intermediate product) which is sintered in a2^(nd) sintering. The use of a crystalline precursor increases thereaction rate between the mixed metal precursor and the lithium source.Thus, the temperature can be lowered. The crystalline precursor is lessreactive so corrosion of the metal tube is reduced. To produce NMC withgood quality and high throughput, a double sintering method isconducted. First, the mixed transition metal source is blended with asource of Li and then sintered. Then, in the 2^(nd) sintering, thecrystalline precursor is mixed with LiOH.H₂O in order to correct theLi/M′ atomic ratio to the final target composition. In consequence, highNi-excess NMC with a low soluble base content is obtained on alarge-scale production through the double sintering method which uses acrystalline precursor.

Manufacturing Example 1 (Prior Art—Counterexample)

The following description gives an example of the standard manufacturingprocedure of NMC powders when applying a conventional direct sinteringprocess which is a solid state reaction between a lithium source,usually Li₂CO₃ or LiOH.H₂O, and a mixed transition metal source, usuallya mixed metal hydroxide M′(OH)₂ or oxyhydroxide M′OOH (with M′=Ni, Mnand Co), but not limited to these hydroxides. In a typicalconfiguration, the direct sintering method comprises the followingsteps:

1) Blending of the mixture of precursors: the lithium source and themixed transition metal source are homogenously blended for 30 minutes bya dry powder mixing process,

2) Sintering the blends in trays: the powder mixture is loaded in traysand sintered at 900° C. for 10 hours under dry air atmosphere in afurnace. The dry air is continuously pumped into the equipment at a flowrate of 20 L/h.

3) Post-treatment: after sintering, the sintered cake is crushed,classified and sieved so as to obtain a non-agglomerate NMC powder.

The direct sintering is generally conducted in a tray based furnace. Forreducing the heat transfer limitation which causes inhomogeneousdistribution of Li component and poor electrochemical performance, a lowtray load is required. The invention observes that the direct sinteringmethod is not applicable for the large scale production of mostNi-excess NMC material (having a Ni-excess z of superior to 0.25) thatdoes not contain an excess of soluble base.

Manufacturing Example 2 (Counterexample)

This example provides a crystalline precursor (lithium deficientsintered precursor) to prepare high Ni-excess NMC on a large-scale bydouble sintering. The process includes among others two sintering steps:

1) 1^(st) blending: to obtain a lithium deficient sintered precursor,Li₂CO₃ and the mixed transition metal source are homogenously blendedfor 30 minutes.

2) 1^(st) sintering: the mixture from the 1^(st) blending step issintered at 900° C. for 10 hours under dry air atmosphere in a traybased furnace. The dry air is continuously pumped into the equipment ata flow rate of 40 L/h. After the 1^(st) sintering, the sintered cake iscrushed, classified, and sieved so as to ready it for the 2^(nd)blending step. The product obtained from this step is a lithiumdeficient sintered precursor, meaning that the Li/M′ atomic ratio inLiM′O₂ is less than 1. The composition of this intermediate product isverified by a standard ICP test.

3) 2^(nd) blending: the lithium deficient sintered precursor is blendedwith LiOH.H₂O in order to correct the Li stoichiometry in theintermediate product to the final target composition ofLi_(1.017)(Ni_(0.4)(Ni_(0.5)Mn_(0.5))_(0.4)Co_(0.2))_(0.983)O₂ (NMC622).

4) 2^(nd) sintering: the blends (from step 3) are sintered at 850° C.for 10 hours under dry air atmosphere in a tray based furnace. The dryair is continuously pumped into the equipment at a flow rate of 40 L/h.

5) Post treatment: after the 2^(nd) sintering, the sintered cake iscrushed, classified, and sieved so as to obtain a non-agglomerated NMCpowder.

Manufacturing Example 3 (Example According to the Invention)

This invention discloses a process to obtain high Ni-excess NMC with alow soluble base content by a double firing method and is illustrated inFIG. 1 . The double firing includes a 1^(st) sintering (F1) whichdelivers an intermediate product (P1), and a second sintering deliveringthe final lithium metal oxide (P2). First, a transition metal precursor(M1) is mixed with a lithium source (L1). Transition metal precursorsare selected from hydroxides, oxyhydroxides, carbonates, mixed oxide,etc. Preferable Ni, Mn, and Co are present and well mixed at atomicscale. The lithium source is selected from lithium hydroxide, lithiumhydroxide hydrate, or lithium oxide. The lithium source is essentiallyfree of Li₂CO₃. Additionally additives (A1) like Al₂O₃, MgO, etc. may beadded for obtaining a doped final material. Additives can be oxides,hydroxides, carbonates, sulfates, etc. A 1^(st) sintering step(F1)—which is the pre-firing—is applied and provides an intermediateproduct (P1). After that, the intermediate product pre-fired product isblended with an additional lithium source (L2). The lithium source isselected from lithium hydroxide, lithium hydroxide hydrate, or lithiumoxide. The lithium source is essentially free of Li₂CO₃. Additionallyadditives or dopants (A2) may be added. A 2^(nd) sintering step(F2)—which is the firing—is applied and provides the final lithiumtransition metal oxide (P2).

For producing an NMC at high throughput with high quality on alarge-scale, the 1^(st) sintering is carried out in a rotary furnace orkiln. This improves the non-uniform Li/M′ atomic ratio effect, and alsoallows very high throughput because the heat transfer issue is resolvedin a rotary furnace. A product in a rotary furnace has a short residencetime. Typical residence times in the heated zone of a rotary furnace areat least 20 minutes and typically less than 3 hours. If the residencetime is too short, the reaction is not complete. If the residence timeis too long, the throughput is insufficient. A typical temperature rangefor the 1^(st) sintering is 650° C. to 850° C. If the temperature is toolow, the reaction is not complete. If the temperature is too high, themetal of the tube tends to react with the lithiated NMC.

The intermediate product has a target Li/M′ atomic range from 0.9 to1.0. The 1^(st) sintering in the rotary furnace uses an oxidizing gas,preferably air. However, if high Ni-excess cathodes are the target,oxygen might be a preferred choice.

During the 2^(nd) sintering, the intermediate product is sintered toachieve the final lithium transition metal oxide. First, theintermediate product is blended with a source of lithium to obtain thefinal Li/M′ atomic ratio target value. Then, the mixture is fired toobtain a well sintered product. The 2^(nd) sintering is typically doneusing ceramic trays and a suitable furnace. Furnaces can be largechamber furnaces where stacks of trays are fired. More suitable areroller hearth kilns where trays with product are carried across thefurnace. Alternatively, pusher kilns can be applied where carts withstacks of trays are carried across the furnace. Other furnace designscan be applied as well. Less desired are rotary furnaces. The rotaryfurnace has a short residence time, which might not allow to achieve awell-sintered high quality product. Another issue linked to rotaryfurnaces are the sintering temperatures. The sintering temperaturesneeded during the 2^(nd) sintering are relatively high, and still highertemperatures would be required if the residence time is short. Undersuch conditions, metal tubes tend to react with lithiated product andmetal corrosion is observed. After the 2^(nd) sintering, NMC powder isachieved having a low soluble base and on a large-scale.

The invention observes that the properties of the intermediated sinteredproduct strongly influence the performance of the final product inbatteries. Particularly, the soluble base content of the final productis strongly related to the conditions during the 1^(st) sintering. The1^(st) sintering temperature, furnace type, tray loading, and the ratioof lithium to the mixed transition metal source can be chosenappropriately to obtain a final product of high quality and with a highthroughput. For example, if the ratio of lithium to metal source is toohigh, the reaction between the mixed transition metal source and thelithium source doesn't finish and results in unreacted and moltenlithium sources, which can attack the inner wall of a furnace. At thesame time, it causes agglomeration of NMC material and uptake of CO₂from the air, which induces a poor cycling performance in batteries. Ifon the contrary the ratio of lithium to metal is too low, a large amountof lithium is required to adjust the Li stoichiometry in theintermediate product to the final target composition during the 2^(nd)sintering. Because the lithium source causes an excess vapor evolutionduring heating, the final product has an inhomogeneous chemicalcomposition. Therefore, the ratio of lithium to metal during the 1^(st)firing must be optimized to produce high quality NMC product. Theproperties of the NMC product using the intermediate sintered precursorwill be checked by various parameters: the crystalline size of theproduct after the 1^(st) sintering step, the Li₂CO₃ content, and thecycling performance of the final product.

Furthermore, to reduce the Li₂CO₃ content in the final NMC material,LiOH.H₂O as lithium source can be used in both of the 1^(st) and the2^(nd) sintering steps. The double sintering using a combination ofrotary and tray based furnace provides the large-scale production of NMCproduct with low soluble base content at low cost. Consequently, thethroughput is much higher compared to the direct sintering methoddescribed in Manufacturing Example 1 and the double sintering method ofManufacturing Example 2 based only on conveyor furnaces. Thus, the useof the lithium deficient sintered precursor and applying the doublefiring method in this invention is less expensive and a more efficientmanufacturing way for Ni-excess NMC.

In this invention, to reduce the soluble base in the final product, themixed transition metal source, which is used during the 1^(st) blendingmay be roasted. It might be useful to reduce the amount of vapor, whichevolves during the first firing. If a mixed hydroxide M′(OH)₂ precursoris roasted at 250° C., for example, then a M′OOH type precursor isachieved which evolves less H₂O. If in another example the precursor isroasted at 375° C., a mixed oxide is predominantly achieved, which doesnot evolve substantial amounts of vapor. The roasting can be performedin air, oxygen, nitrogen, or a dynamic vacuum. The roasted mixedtransition metal source is blended with LiOH.H₂O and then sintered forthe formation of a lithium deficient sintered precursor. When using theroasted mixed transition metal oxide, a final NMC material with lowsoluble base content is obtained in a large-scale production.

During the 1^(st) sintering, the firing time may also be optimized toguarantee the reaction processing forward to the maximum extent. In anembodiment, the total sintering time including heating and cooling isset in the range of 12 to 20 hours for the large-scale production ofNMC. After the 1^(st) sintering, an intermediate sintered product isobtained. The product has a low content of Li₂CO₃ impurity. In anembodiment, it is determined by pH titration that the Li₂CO₃ content isless than 0.40 wt %, preferably less than 0.20 wt %. The intermediateproduct is a single phase lithium transition metal oxide having anordered or disordered rock salt crystal structure. The composition isbelieved to be Li_(1-a)M′_(1+a)O₂. In an embodiment the Li/M′stoichiometric ratio is from 0.85 to 1.0, preferably from 0.9 to 1.0.The metal composition isLi_(1-a)((Ni_(z)(Ni_(0.5)Mn_(0.5))_(y)Co_(x))_(1-k)A_(k))_(1+a) O₂,wherein x+y+z=1, 0.05≤x≤0.40, 0.25≤z≤0.85, A is a dopant, 0≤k≤0.10, and0.00≤a≤0.053. The precursor has a crystalline size L expressed in nmthat is dependent on the Ni-excess content z, with 25≤L≤36. The dopantmay be either one or more of Mg, Al, Ca, Si, B, W, Zr, Ti, Nb, Ba, andSr. These dopants can contribute to an improvement of the performanceand safety of a battery containing the final cathode material made fromthe precursor.

In this invention, the double sintering method using a rotary furnacefor the 1^(st) sintering increases the throughput of NMC, and uses muchless space than a conveyor furnace. As the investment cost roughlycorrelates with the required space, the investment for the rotaryfurnace is much less than that of the conveyor furnace. Moreover, theprecursor and lithium source can be filled easily and unloaded in therotary furnace, whereas the conveyor furnace usually requires a complextray filling equipment. Therefore, to use the double sintering methodbased on the rotary furnace for the 1^(st) sintering enhances thethroughput of the final NMC product and reduces the investment costdramatically.

Surface Coating Example 1

Referring back to FIG. 1 , an aluminum coated NMC is obtained byblending and sintering a final lithium transition metal oxide powder(F3) and for example an aluminum source (A3). The aluminum source inthis step can be a metal oxide (Al₂O₃) that may be combined with acompound selected from the group consisting of TiO₂, MgO, WO₃, ZrO₂,Cr₂O₃, V₂O₅, and mixtures thereof. The preferred source of aluminum is ananometric alumina powder, for example fumed alumina. In the heatingstep, the mixture is heated at about 750° C. The sintering time ispreferably at least 3 hours, more preferably at least 5 hours. The finalproduct may have an Al content more than 0.3 mol % but less than 3.0 mol%.

Surface Coating Example 2

Referring back to FIG. 1 , an aluminum and fluorine coated NMC isobtained by blending and subsequent sintering (F3) using an aluminumsource (as described before) and a fluorine-containing polymer (A3). Atypical example for such a polymer is a PVDF homopolymer or PVDFcopolymer (such as HYLAR® or SOLEF® PVDF, both from Solvay SA, Belgium).Another known PVDF based copolymer is for example a PVDF-HFP(hexa-fluoro propylene). Such polymers are often known under the name“Kynar®”. Teflon—or PTFE—could also be used as polymer. For thesintering step, the sintering temperature of the mixture is at least250° C., preferably at least 350° C. The sintering time here ispreferably at least 3 hours, more preferably at least 5 hours. In thesintering step, the crystalline structure of the fumed alumina ismaintained during the coating process and is found in the coating layersurrounding the lithium metal oxide core. Also, the fluorine-containingpolymer is completely decomposed and lithium fluoride is formed, whichis found in the surface layer of the particles. The obtained surfacelayer has the following function: the thin layer comprising LiF replacesthe reactive surface base layer, thus reducing the base contentpractically to zero at the core's surface, and improving the overallsafety.

Surface Coating Example 3

Referring back to FIG. 1 , an aluminum and sulfate coated NMC isobtained by blending and subsequent sintering (F3) using an aluminumsource (as described before) and a sulfur-containing source (A3). Thesulfur-containing source in this step can be either one of Li₂S₂O₈,H₂S₂O₈ and Na₂S₂O₈. In the sintering step, the blend is heated between300° C. and 500° C.—and preferably 375° C.—under air. The sintering timeis at least 3 hours, and preferably at least 5 hours. The final productcontains a coating of a sulfate and aluminum, which improves batteryperformance by decomposition of soluble surface base compounds.

Description of Analysis Methods:

A) pH Titration Test

The soluble base content is a material surface property that can bequantitatively measured by the analysis of reaction products between thesurface and water, as is explained in WO2012-107313. If powder isimmersed in water, a surface reaction occurs. During the reaction, thepH of the water increases (as basic compounds dissolve) and the basecontent is quantified by a pH titration. The result of the titration isthe “soluble base content” (SBC). The content of soluble base can bemeasured as follows: 2.5 g of powder is immersed in 100 ml of deionizedwater and stirred for 10 minutes in a sealed glass flask. After stirringto dissolve the base, the suspension of powder in water is filtered toget a clear solution. Then 90 ml of the clear solution is titrated bylogging the pH profile during addition of 0.1M HCl at a rate of 0.5ml/min until the pH reaches 3 under stirring. A reference voltageprofile is obtained by titrating suitable mixtures of LiOH and Li₂CO₃dissolved in low concentration in deionized water. In almost all cases,two distinct plateaus are observed. The upper plateau with endpoint γ1(in ml) between pH 8˜9 is the equilibrium OH⁻/H₂O followed by theequilibrium CO₃ ²⁻/HCO₃ ⁻, the lower plateau with endpoint γ2 (in ml)between pH 4˜6 is HCO³⁻/H₂CO₃. The inflection point between the firstand second plateau γ1 as well as the inflection point after the secondplateau γ2 are obtained from the corresponding minima of the derivatived_(pH)/d_(Vol) of the pH profile. The second inflection point generallyis near to pH 4.7. Results are then expressed in LiOH and Li₂CO₃ weightpercent as follows:

${{Li_{2}CO_{3}{wt}\%} = {\frac{7{3.8}909}{1000} \times \left( {\gamma_{2} - \gamma_{1}} \right)}};$${{LiOH}{wt}\%} = {\frac{23.9483}{1000} \times {\left( {{2 \times \gamma_{1}} - \gamma_{2}} \right).}}$

B) Valence State Titration Test

In this invention, the average valence state of products is determinedby auto-titration using a Mettler Toledo Autotitrator DL70ES. Thetitrant is freshly made potassium dichromate water solution with aconcentration of 0.01493 mol/L. Prior to titrant preparation, K₂Cr₂O₇ isdried at 104° C. for at 2 hours. The reducing agent is freshly preparedferrous ammonium sulfate water solution. First, 156.85 g Fe(NH₄)₂(SO₄)₂is weighed in a beaker. About 250 mL of nano-pure water and about 5 mLof 1:1 sulfuric acid are added. Heat may be applied to speed up thedissolution process. Afterwards, the solution is transferred into a 1 Lvolumetric flask and diluted to marked volume at 20° C. before use.

0.5 g to 3.0 g of NMC precursor sample is weighed into a digestion tube.20 mL of freshly made Fe(NH₄)₂(SO₄)₂ solution and 10 mL of concentratedHCl are added into the digestion tube. Heat may be applied here forcomplete digestion of the sample. The solution is fully transferred intoa 100 mL volumetric flask and diluted to the volume mark at 20° C.Afterwards, 10 mL of this solution is pipetted into a titration cuptogether with 5 mL of 1:1 HCl and 40 mL of nano-pure water to the cup.The NMC precursor sample solution is now ready for valence titration.The same procedure is repeated to prepare a reference sample solution(without NMC precursor) using exactly the same amount of Fe(NH₄)₂(SO₄)₂solution, concentrated HCl, 1:1 HCl, nano-pure water under similarconditions. Using the above prepared K₂Cr₂O₇ solution, both NMCprecursor sample solution and reference sample solution are titrated byusing Mettler Toledo Autotitrator DL70ES. The volume of titrant consumedare recorded for each titration. The difference in volume is used forvalence state calculation.

C) Karl Fischer Titration Test

The typical moisture content of precursor samples after drying is below1 wt %, is determined by Karl Fischer at 250° C. KF 34739-Coulomat AGOven is used as a reagent and added until the water in the samples isremoved.

D) X-Ray Diffraction Test

The X-ray diffraction (XRD) pattern of a crystalline precursor powdersample is collected with a Rigaku X-Ray Diffractometer (Ultima IV) usinga Cu Kα radiation source (40 kV, 40 mA) emitting at a wavelength of1.5418 Å. The instrument configuration is set at: a 1° Soller slit (SS),a 10 mm divergent height limiting slit (DHLS), a 1° divergence slit(DS), and a 0.3 mm reception slit (RS). The diameter of the goniometeris 185 mm. Diffraction patterns are obtained in the 20 range from 15° to85° with a scan speed of 1.0° per minute and a step-size of 0.02° perscan.

In the present invention, the crystallite size L, expressed in nm, isobtained through the analysis of the width of individual diffractionpeaks by the following Williamson-Hall (W-H) method. As described in‘Acta Metallurgica, 1953, VOL1, 22-31’, Williamson and Hall proposed amethod to extract the information on a crystallite size from the fullwidth of half maximum (FWHM; β) of diffraction peaks. The detailedcalculation method for estimating crystallite size follows that of‘Journal of Theoretical and Applied Physics, 2012, 6:6, Page 2 to 3 of8’.

The FWHM of any diffraction peak can be described as a linearcombination of the contributions from the lattice strain and thecrystallite size through the Williamson-Hall (W-H) equation:

${\beta\cos\theta} = {\frac{k\lambda}{L} + {4\varepsilon\sin\theta}}$

-   -   β: FWHM (in radians)    -   λ: X-ray wavelength (CuKα=1.5418 Å)    -   θ: bragg angle (°)    -   L: crystallite size (nm)    -   ε: strain    -   K: constant, 0.9

A plot is drawn with 4 sin θ along the x-axis and β cos θ along they-aixs using the XRD data on the peak (003) and the peak (104). The peak(003) and the peak (104) are at 17.0° to 20.2° and 43.0° to 45.5°. Fromthe linear fit to the data, the crystalline size (L) was estimated fromthe y-intercept. Accordingly, W-H equation is converted to the followingequation in the present patent.

A crystallite size L, expressed in nm, is calculated according to theWilliamson-Hall equation:

$L = \frac{K\lambda}{y_{2} - {\frac{y_{2} - y_{1}}{x_{2} - x_{1}} \times x_{2}}}$

-   -   x1: sin θ₁ of the peak (003) of a R-3m space group from 17.0° to        20.0°, θ₁ is a half of 2θ₁, wherein 2θ₁ is the center of the        peak (003)    -   x2: sin θ₂ of the peak (104) of a R-3m space group from 43.0° to        45.5°, θ₂ is a half of 2θ₂, wherein 2θ₂ is the center of the        peak (104)    -   y1: the product of β₁ and cos θ₁ of the peak (003) of a R-3m        space group from 17.0° to 20.0°, wherein β₁ is FWHM, expressed        in °, θ₁ is a half of 2θ₁, wherein 2θ₁ is the center of the peak        (003)    -   y2: the product of β₂ and cos θ₂ of the peak (104) of a R-3m        space group from 43.0° to 45.5°, wherein β₂ is FWHM, expressed        in °, θ₂ is a half of 2θ₂, wherein 2θ₂ is the center of the peak        (104)

θ and β are obtained by a nonlinear curve fitting method in Origin 9.1software with the Lorentz model. Kα2 peaks are not considered as a partof the peak.

LaB₆ (Lanthanum hexaboride) is used as a standard material in order tocalibrate an instrumental broadening of diffraction peaks. The (011)peak in the range from 28° to 32° of the LaB₆ powder has FWHM (β) of0.1264° and 2θ (center of the peak) of 30.3719°. The (111) peak in therange from 36° to 39° of the LaB₆ powder has β of 0.1357° and 2θ (centerof the peak) of 37.4318°. Therefore, the calculated crystallite sizefrom the (011) peak and (111) peak of the LaB₆ powder is 85.5 nm. Sincethe instrumental peak broadening affects β significantly, the instrumentshould be calibrated so as to provide abovementioned crystallite sizesof LaB₆ powder.

It is known that the structural model ofLi_(1-a)((Ni_(z)(Ni_(0.5)Mn_(0.5))_(y)Co_(x))_(1-k)A_(k))_(1+a)O₂ is theα-NaFeO₂ structure (space group R-3m, no. 166) with Li in 3a sites, Ni,Co, and Mn randomly placed on 3b sites, and oxygen atoms on 6c sites (ingeneral an NMC compound can be represented as [Li]_(3a)[Ni_(x)Co_(y)Mn_(z)]_(3b)[O₂]_(6c)). The current invention howeverobserves that the lithium deficient sintered precursor has a phenomenonof cation mixing, meaning that there is a high amount of Ni on Li 3asites (being the sites within the layers predominantly filled by Liatoms). This differentiates our lithium deficient sintered precursorfrom the common lithium deficient material obtained duringcharge/discharge. The latter basically has little cation mixing.Generally, the degree of Li/M disorder can be roughly estimated by theintensity ratio of peak (003) (referred to as I003) to I104 (=intensityof peak (104)), as indicated in ‘J. Electrochem. Soc.140 (1993) 1862’. Alarge ratio of 1003 to 1104 means a low degree of Li/M′ disorder. Asystematic study on cation mixing was described by Jeff Dahn in SolidState Ionics 44 (1990) 87-97. U.S. Pat. No. 6,660,432 B2 gives anextended application of this method to evaluate the degree of Li/Mdisorder on Li-in excess transition metal oxide material. The idea ofthis method originates from the fact that the intensity I101 of peak(101) at 35° to 37.2° is rapidly attenuated while the combinationalintensity of peaks (006) and peak (102) at 37.2° to 39.2° (I006 & I102)are enhanced when Ni atoms occupy “Li sites”. Thus, a factor of R isintroduced, which represents the ratio of I006 & I102 to I101. In Dahn'spaper, it is demonstrated that the R factor increases rapidly as xdecreases in Li_(x)Ni_(2-x)O₂ material, where 1-x refers to the degreeof cation mixing. A formula was deducted to express the relationshipbetween R and x as follows:

$R = {\frac{4}{3}\frac{\left( {{1.6} - x} \right)^{2}}{x^{2}}}$

So the degree of cation mixing (1-x) is equivalent to R, and can bedetermined from the R value according to the formula.

In this invention, the two methods here above are used to evaluate thedegree of cation mixing of the lithium deficient sintered precursors andthe final products based on these precursors. The ratio I003/I104 andthe value of R will be discussed below. It is observed that the degreeof cation mixing is higher in a lithium deficient sintered precursor bycontrast to the final product. Note that to calculate the ratioI003/I104 and the value of R, integrated XRD peaks are used.

E) Coin Cell Test

Coin cells are assembled in a glovebox which is filled with an inert gas(argon). A separator (Celgard 2320) is located between the positiveelectrode and a piece of lithium foil used as negative electrode. 1MLiPF₆ in EC/DMC (1:2 in volume) is used as electrolyte, dropped betweenseparator and electrodes. Each cell is cycled at 25° C. usingToscat-3100 computer-controlled galvanostatic cycling stations (fromToyo). The coin cell testing schedule used to evaluate NMC samples isdetailed in Table 1. The schedules use a 1C current definition of 160mA/g or 220 mAh/g and comprise three parts as follows:

Part I is the evaluation of rate performance at 0.1C, 0.2C, 0.5C, 1C,2C, and 3C in the 4.3˜3.0V/Li metal window range. With the exception ofthe 1^(st) cycle where the initial charge capacity CQ1 and dischargecapacity DQ1 are measured in constant current mode (CC), all subsequentcycles feature a constant current-constant voltage during the chargewith an end current criterion of 0.05C. A rest time of 30 minutes forthe first cycle and 10 minutes for all subsequent cycles is allowedbetween each charge and discharge. The irreversible capacity Q_(irr). isexpressed in % as:

$Q_{{Irr}.} = {\frac{\left( {{CQ1} - {DQ1}} \right)}{CQ1} \times 100(\%)}$

The rate performance at 0.2C, 0.5C, 1C, 2C and 3C is expressed as theratio between the retained discharge capacity DQn, with n=2, 3, 4, 5 and6 for respectively nC=0.2C, 0.5C, 1C, 2C and 3C as follows:

${{nC} - {rate}} = {\frac{DQn}{DQ1} \times 100(\%)}$

For example,

${{3C} - {{rate}\left( {{in}{}\%} \right)}} = {\frac{{DQ}6}{DQ1} \times 100}$

Part II is the evaluation of cycle life at 1C. The charge cutoff voltageis set as 4.3 or 4.5V/Li metal. The discharge capacity at 4.3 or 4.5V/Limetal is measured at 0.1C at cycles 7 and 34 and 1C at cycles 8 and 35.Capacity fadings at 0.1C and 1C are calculated as follows and areexpressed in % per 100 cycles:

${0.1C{{QFad}.}} = {\left( {1 - \frac{DQ34}{DQ7}} \right) \times \frac{10000}{27}{in}{\%/100}{cycles}}$

${0.1C{{QFad}.}} = {\left( {1 - \frac{{DQ}35}{{DQ}8}} \right) \times \frac{10000}{27}{in}{\%/100}{cycles}}$

Energy fadings at 0.1C and 1C are calculated as follows and areexpressed in % per 100 cycles. Vn is the average voltage at cycle n.

${0.1C{{EFad}.}} = {\left( {1 - \frac{{DQ}34 \times \overset{\_}{V34}}{{DQ}7 \times \overset{\_}{V7}}} \right) \times \frac{10000}{27}{in}{\%/100}{cycles}}$${0.1C{{EFad}.}} = {\left( {1 - \frac{{DQ}35 \times \overset{\_}{V35}}{{DQ}8 \times \overset{\_}{V8}}} \right) \times \frac{10000}{27}{in}{\%/100}{cycles}}$

Part III is an accelerated cycle life experiment using 1C-rate for thecharge and 1C rate for the discharge between 4.5 and 3.0V/Li metal.Capacity and energy fading are calculated as follows:

${1{C/1}C{}{{QFad}.}} = {\left( {1 - \frac{{DQ}60}{{DQ}36}} \right) \times \frac{10000}{27}{in}{\%/100}{cycles}}$${1{C/1}C{{EFad}.}} = {\left( {1 - \frac{{DQ}60 \times \overset{\_}{V60}}{{DQ}36 \times 36}} \right) \times \frac{10000}{27}{in}{\%/100}{cycles}}$

TABLE 1 coin cell testing procedure Charge Discharge Cycle C End RestV/Li C End Rest V/Li Type No Rate current (min) metal (V) Rate current(min) metal (V) Part I 1 0.10 — 30 4.3 0.10 — 30 3.0 2 0.25 0.05 C 104.3 0.20 — 10 3.0 3 0.25 0.05 C 10 4.3 0.50 — 10 3.0 4 0.25 0.05 C 104.3 1.00 — 10 3.0 5 0.25 0.05 C 10 4.3 2.00 — 10 3.0 6 0.25 0.05 C 104.3 3.00 — 10 3.0 Part II 7 0.25 0.1 C 10 4.3 or 4.5 0.10 — 10 3.0 80.25 0.1 C 10 4.3 or 4.5 1.00 — 10 3.0  9~33 0.50 0.1 C 10 4.3 or 4.51.00 — 10 3.0 34  0.25 0.1 C 10 4.3 or 4.5 0.10 — 10 3.0 35  0.25 0.1 C10 4.3 or 4.5 1.00 — 10 3.0 Part III 36~60 1.00 — 10 4.3 or 4.5 1.00 —10 3.0

The following examples illustrate the present invention in more detail.

Explanatory Example 1: NMC Samples Prepared Using Direct and DoubleSintering

An NMC powder is prepared according to the above-mentioned“Manufacturing Example 1” with Li₂CO₃ as Li source. This sample islabelled NMC P1.1. Also, NMC powder is prepared as in “ManufacturingExample 2”, based on a conveyor furnace for the 1^(st) and 2^(nd)sintering, and is labelled NMC P1.2. Finally, NMC powder is prepared bythe “Manufacturing Example 2”, but using a rotary furnace during the1^(st) sintering and is labelled NMC P1.3. In all the Examples of thisinvention, mixed nickel-manganese-cobalt hydroxides (M′-hydroxides,where M′=Ni_(0.6)Mn_(0.2)Co_(0.2) unless otherwise mentioned) are usedas precursors, where M′-hydroxide is prepared by a co-precipitation inlarge scale continuous stirred tank reactor (CSTR) with mixednickel-manganese cobalt sulfates, sodium hydroxide, and ammonia. In thiscase, the general formula of the M′-hydroxide is(Ni_(0.4)(Ni_(0.5)Mn_(0.5))_(0.4)Co_(0.2))(O)_(v)(OH)_(2-v), with 0≤v≤1.

FIG. 2 presents the pH titration results of these NMC materials, wherethe weight percentage of lithium carbonate in the final NMC samples isplotted. The prepared powders have a large distinction in base content.NMC P1.2 sample has less lithium carbonate than NMC P1.1 because of theused double sintering method combined with a Li deficient precursor. Asmentioned above, although a rotary furnace for the 1^(st) sintering stepduring the double sintering method is suitable for a large-scaleproduction of NMC, NMC P1.3 sample has a higher residual lithiumcarbonate content than the other two samples. Therefore, it is useful toinvestigate if LiOH.H₂O instead of Li₂CO₃ as a lithium source for the1^(st) sintering can reduce the soluble base content by its lowerthermodynamic stability during the preparation of NMC, leading to goodelectrochemical performance. The following examples will illustrate thisin detail.

Explanatory Example 2: NMC Samples Prepared Using Pretreated TransitionMetal Source and Direct Sintering

An NMC powder is prepared based on a direct sintering method using apristine mixed transition metal hydroxide type source and LiOH.H₂O. Thissample was prepared on small scale and is labelled NMC P2.1. Another NMCpowder is prepared using a pretreated mixed transition metal source on alarge-scale using direct sintering, and is labelled NMC P2.2. For thepretreatment of the metal source, a mixed transition metal oxide isheated at 150° C. under N₂ atmosphere in an oven. Finally, an NMC powderis manufactured using the same step in NMC P2.2, except that the heatingtemperature of the pretreated metal source is 250° C. It is labelled NMCP2.3. To investigate also the properties of pretreated transition metalsources themselves, we labelled the transition metal sourcesrespectively NMC P2.1a (not heated), NMC P2.2a (heated at 150° C.), andNMC P2.3a (heated at 250° C.). FIG. 3 indicates the XRD patterns of thepretreated transition metal samples. After heating, the XRD peaks of thesources shifted, which means the oxidation state changed. In Table 2,the properties of the pretreated transition metal samples are shown indetail. The values of oxidation state are calculated using a ‘Valencestate titration’ method.

TABLE 2 Properties of pretreated transition metal samples Oxidationstate H₂O Mass loss Sample (n⁺) (%) (%) NMC P2.1a 2.17 17.413 — NMCP2.2a 2.53 12.605 0.89% NMC P2.3a 2.71 2.805 9.49%

NMC P2.1a has an oxidation state of 2.17, corresponding to the formula(Ni_(0.4)(Ni_(0.5)Mn_(0.5))_(0.4)Co_(0.2))(O)_(0.17)(OH)_(1.83). Afterheating at 150° C., the oxidation state of NMC P2.2a is 2.53, and theformula becomes(Ni_(0.4)(Ni_(0.5)Mn_(0.5))_(0.4)Co_(0.2))(O)_(0.53)(OH)_(1.47). Theoxidation state of NMC P2.3a is 2.71, and the formula becomes(Ni_(0.4)(Ni_(0.5)Mn_(0.5))_(0.4)Co_(0.2))(O)_(0.71)(OH)_(1.29). Byincreasing the pretreatment temperature, the transition metal source hasa higher oxidation state than pristine source. Also, to investigate themoisture content of the pretreated precursors, their H₂O content isanalyzed after being heated at 300° C. NMC P2.3a has the lowest moisturecontent. By increasing the heating temperature, the mass loss of theprecursor increases, compared to the initial weight. Table 3 summarizesthe pH titration and coin cell results of NMC P2.1, P2.2, and P2.3. Thecoin cell test is conducted at the charge cutoff voltage of 4.5V/Limetal and a 1C current definition of 160 mA/g.

TABLE 3 Performance of Explanatory Example 2 DQ0.1 C 0.1 C QFad. 1 CQFad. Li₂CO₃ Sample (mAh/g) (%/100) (%/100) (wt %) NMC P2.1 178.4 1.55.9 0.138 NMC P2.2 174.3 4.4 10.2  0.306 NMC P2.3 175.0 3.2 9.0 0.229

The weight percentage of lithium carbonate in the final NMC P2.2 sampleis determined at 0.306 wt %, which is a high amount compared to thecontent of NMC P2.1. Because the NMC product is prepared by directsintering on a large-scale, it contains large amounts of lithiumcarbonate. Thus, by using a roasted transition metal source with low H₂Ocontent the amount of soluble base may be reduced, as is shown for theNMC P2.3 sample.

The presence of high soluble base and Li₂CO₃ contents in the final NMCmaterial generally deteriorates the cycling performance. The coin celltest evaluates the cycle stability of NMC P2.1, NMC P2.2, and NMC P2.3samples based on the capacity fade at 0.1C and 1C. It shows that the NMCP2.1 sample has 0.015% loss of discharge capacity per cycle at 0.1 Cafter 25 cycles and 0.059% loss for 1C. The NMC P2.2 sample has 0.044%loss of discharge capacity per cycle at 0.1C after 25 cycles and 0.102%loss for 1C. When the heated mixed transition metal oxide at 150° C. isused as a metal source for large-scale production, it shows the worsecycling performance due to its high lithium carbonate content. Moreover,in case of NMC P2.3 prepared using the pretreated metal source at 250°C., it has a better cycle stability than NMC P2.2. Therefore, for thelarge-scale production, it is possible to produce NMC with enhancedbattery performance by using a high-temperature pretreated transitionmetal source.

Example 1: NMC Samples Prepared Using Double Sintering

An NMC powder with formula Li_(1.017)M′_(0.983)O₂ withM′=Ni_(0.4)(Ni_(0.5)Mn_(0.5))_(0.4)Co_(0.2) is manufactured from anintermediate product with a Li/M′ atomic ratio of 0.921 through theabove-mentioned “Manufacturing Example 3”: steps F1 and F2.

In the 1^(st) sintering step, LiOH.H₂O is used as lithium precursor toproduce the intermediate product in a rotary furnace. The mixture oftransition metal source and lithium precursor is sintered at 820° C. for2 hours of residence time and 1.316 rpm of rotation speed under dry airwith a rate of 2 m³/kg. The 2^(nd) sintering is conducted at 860° C. for10 hours under dry air atmosphere in a tray based furnace. The dry airis continuously pumped into the equipment at a flow rate of 40 L/h. Theabove prepared lithium deficient sintered precursor after the 1^(st)sintering is labelled NMC E1p, and the final NMC sample after 2^(nd)sintering is labelled NMC E1.

FIG. 4 shows the XRD patterns of NMC E1p and NMC E1. The Bragg peaks(003), (101), (104) and doublet peak (006, 102) in that order are thehighest in the patterns. Based on the intensity of these peaks, Table 4summarizes the ratio of I003/I104 and R factor of the NMC E1p and E1samples.

TABLE 4 I003/I104 ratio and R factor of Example 1 Sample I003/I104 Rfactor NMC E1p 0.87 0.60 NMC E1 1.02 0.40

As described above, the ratio of I003/I104 reflects the degree of Li totransition metal disorder. A large value of I003/I104 indicates a smalldegree of distortion. The intermediate product sample NMC E1p has asmall I003/I104 ratio, which means there is more cation mixing in NMCE1p and more Ni on the Li sites. The same observation can be made whencomparing the R factor. The intermediate product has a higher R factorby contrast to the final product. As discussed in Dahn's paper mentionedabove, a high R factor means a high disordering of Li and transitionmetals. Thus, the higher value of R in NMC E1p confirms that there is ahigher percentage of Ni on Li sites in the intermediate product. Table 5summarizes the electrochemical performance and soluble base content ofNMC E1. The coin cell test is conducted at the charge cutoff voltage of4.5V/Li metal and a 1C current definition of 160 mA/g.

TABLE 5 Performance of Example 1 DQ0.1 C 0.1 C QFad. 1 C QFad. Li₂CO₃Sample (mAh/g) (%/100) (%/100) (wt %) NMC E1 179.5 0.8 5.4 0.206

The NMC E1 sample contains much less weight percentage of lithiumcarbonate than NMC P1.1, P1.2, and P1.3. It shows that there is 0.008%loss of discharge capacity per cycle at 0.1C after 25 cycles and 0.054%loss for 1C.

Comparative Example 1: NMC Samples Prepared Using Roasted TransitionMetal Source and Double Sintering

An NMC powder with formula Li_(1.017)M′_(0.983)O₂ withM′=Ni_(0.4)(Ni_(0.5)Mn_(0.5))_(0.4)Co_(0.2) is prepared using the stepsin Example 1, except that the intermediate product has a Li/M′ atomicratio of 0.885 and that the mixed transition metal source is used afterroasting at 250° C. under N₂ atmosphere in an oven for 24 hours. In the1^(st) sintering step, the mixture of transition metal source andLiOH.H₂O is sintered at 820° C. for 2 hours of residence time and 0.628rpm of rotation speed under dry air with flow rate of 1.67 m³/kg in arotary furnace. The 2^(nd) sintering is conducted at 865° C. for 10hours under dry air atmosphere in a tray based furnace. The dry air iscontinuously pumped into the equipment at a flow rate of 40 L/h. Theabove prepared intermediate product after 1^(st) sintering is labelledNMC cE1p, and the final NMC sample after 2^(nd) sintering is labelledNMC cE1. FIG. 5 shows the XRD patterns of NMC cE1p and NMC cE1. TheBragg peaks (003), (101), (104) and doublet peak (006, 102) are clearlyvisible. Based on the intensity of these peaks, Table 6 summarizes theratio of I003/I104 and R factor of the NMC cE1p and NMC cE1 samples.

TABLE 6 I003/I104 ratio and R factor of Comparative Example 1 SampleI003/I104 R factor NMC cE1p 0.81 0.66 NMC cE1 1.00 0.41

Looking at the ratio I003/I104, it can be concluded that there is morecation mixing in NMC cE1p and more Ni on the Li sites. The sameobservation can be made when comparing the R factor. The higher value ofR in NMC cE1p confirms that there is a higher percentage of Ni on Lisites in the intermediate product. Table 7 summarizes theelectrochemical performance and soluble base content of NMC cE1. Thecoin cell test is conducted at the charge cutoff voltage of 4.5V/Limetal and a 1C current definition of 160 mA/g.

TABLE 7 Performance of Comparative Example 1 DQ0.1 C 0.1 C QFad. 1 CQFad. Li₂CO₃ Sample (mAh/g) (%/100) (%/100) (wt %) NMC cE1 176.7 0.2 5.40.196

The NMC cE1 sample shows less weight percentage of lithium carbonatethan NMC P1.1, P1.2, and P1.3. It shows that there is 0.002% loss ofdischarge capacity per cycle at 0.1C after 25 cycles and 0.054% loss for1C. Therefore, the double sintering method using the roasted transitionmetal source enhances the cycle properties of the NMC product.

Comparative Example 2: NMC Samples Prepared Using the IntermediateProduct with Low Li/M′ Atomic Ratio

An NMC powder having the formula Li_(1.017)M′_(0.983)O₂ withM′=Ni_(0.4)(Ni_(0.5)Mn_(0.5))_(0.4)Co_(0.2) is obtained according to thesteps in Comparative Example 1 (including the pre-roasting step), exceptthat the intermediate product has a Li/M′ atomic ratio of 0.718. In the1^(st) sintering step, the mixture of transition metal source andLiOH.H₂O is sintered at 820° C. for 2 hours of residence time and 0.628rpm of rotation speed under dry air with flow rate of 1.67 m³/kg in arotary furnace. The 2^(nd) sintering is conducted at 855° C. for 10hours under dry air atmosphere in a tray based furnace. The dry air iscontinuously pumped into the equipment at a flow rate of 40 L/h. Theabove prepared intermediate product after the 1^(st) sintering islabelled NMC cE2p, and the final NMC sample after the 2^(nd) sinteringis labelled NMC cE2.

Comparative Example 3: NMC Samples Prepared Using the IntermediateProduct with Low Li/M′ Atomic Ratio at Low Temperature

An NMC powder with formula Li_(1.017)M′_(0.983)O₂ withM′=Ni_(0.4)(Ni_(0.5)Mn_(0.5))_(0.4)Co_(0.2) is prepared according to thesteps in Comparative Example 1 (including the pre-roasting step), exceptthat the lithium deficient sintered precursor has a ratio ofLi/M′=0.723, as it is prepared at a low 1^(st) sintering temperature of720° C. In the 1^(st) sintering step, the mixture of transition metalsource and LiOH.H₂O is sintered at 720° C. for 2 hours of residence timeand 0.628 rpm of rotation speed under dry air with flow rate of 1.67m³/kg in a rotary furnace. The 2^(nd) sintering is conducted at 845° C.for 10 hours under dry air atmosphere in a tray based furnace. The dryair is continuously pumped into the equipment at a flow rate of 40 L/hr.The above prepared intermediate product after 1^(st) sintering islabelled NMC cE3p, and the final NMC sample after 2^(nd) sintering islabelled NMC cE3.

FIG. 6 shows the X-ray diffraction patterns of NMC cE2p and NMC cE3p,where the intermediate means the intermediate powder obtained after the1^(st) sintering. The XRD patterns disclose single-phase NMC powderswithout obvious impurities. In the Figure, the (003) and (104)diffraction peaks are used to calculate the crystalline size L andlattice strain with the W-H method. FIG. 7 shows the coin cell resultsof the NMC cE2 and NMC cE3 samples, where the square symbol is for NMCcE2 and the circle symbol is for NMC cE3. It can be observed that theNMC cE3 has a similar but slightly better cycling stability than NMCcE2, and Table 8 summarizes the electrochemical performance and solublebase content of NMC cE2 and NMC cE3. The coin cell test is conducted atthe charge cutoff voltage of 4.5V/Li metal and a 1C current definitionof 160 mA/g.

TABLE 8 Performance of Comparative Example 2 and Comparative Example 3*Size (nm) DQ0.1 C 0.1 C QFad. 1 C QFad. Li₂CO₃ Sample by W-H (mAh/g)(%/100) (%/100) (wt %) NMC cE2 33.8 179.0 4.0 8.7 0.245 NMC cE3 31.1176.5 2.2 7.4 0.256 *The crystalline size L of the intermediateproducts.

These samples were made using the same double firing method, the onlydifference being the different sintering temperature conditions in the1^(st) sintering, which results in a different crystalline size andlattice strain of the intermediate precursor. When fabricated at a low1^(st) sintering temperature of 820° C., NMC cE2 has a crystalline sizeof 33.8 nm. When the sintering temperature goes down by 100° C., thecrystalline size of NMC cE3 is 31.1 nm.

Example 2: NMC Samples Prepared Using a High Tray Load During the 2^(nd)Sintering

An NMC powder with formula Li_(1.017)M′_(0.983)O₂ withM′=Ni_(0.4)(Ni_(0.5)Mn_(0.5))_(0.4)Co_(0.2) is prepared using the stepsof Example 1, except that the intermediate product has a Li/M′ atomicratio of 0.93, and is prepared with a high tray load of 7 kg during the2^(nd) sintering. The amount of blend on the tray is twice as much asthe Example 1, where it was 3.5 kg. Table 9 summarizes theelectrochemical performance and soluble base content of NMC E2. The coincell test is conducted at the charge cutoff voltage of 4.5V/Li metal anda 1C current definition of 160 mA/g.

TABLE 9 Performance of Example 2 DQ0.1 C 0.1 C QFad. 1 C QFad. Li₂CO₃Sample (mAh/g) (%/100) (%/100) (wt %) NMC E2 174.8 −0.3 4.1 0.315

The NMC E2 sample shows a higher weight percentage of lithium carbonatethan other NMC samples because the NMC material is prepared with a hightray load. Nevertheless, it exhibits good electrochemical performances,as it does not show a loss of discharge capacity per cycle at 0.1C after25 cycles, and 0.041% loss for 1C. Therefore, by using the double firingmethod according to the invention, it is possible to obtain anickel-excess NMC powder having good cycling stability even inlarge-scale manufacturing.

Example 3: Al Coated NMC Samples

An Al coated NMC sample NMC E3 is obtained using the steps in Example 1and “Surface Coating Example 1”. After blending with a nanometricalumina powder (2 g alumina per kg NMC), homogeneous blending, andsintering at 750° C. (the dwell time being around 5 hours), NMC powderis surrounded by an Al layer on the surface.

Example 4: Al/F Coated NMC Samples

An Al/F coated NMC sample NMC E4 is obtained using the steps in Example1 and “Surface Coating Example 2”: 1 kg of NMC powder is filled into amixer, 2 g of alumina (Al₂O₃) powder and 3 g polyvinylidene fluoride(PVDF) powder is added as well. After homogeneously mixing (usually 30minutes at 1000 rpm), the mixture is sintered in a box furnace in anoxidizing atmosphere. The sintering temperature is 375° C. and the dwelltime is 5 hours. As a result, the NMC powder has an Al/F layer on thesurface.

FIG. 8 shows the coin cell results of the NMC E3 and NMC E4 samples,where the square symbol is for NMC E3 and the circle symbol is for NMCE4. The cycling stability of NMC E6 is excellent, and from the Figure,it can be observed that the NMC E4 has an even better discharge capacityand cycling stability than NMC E3. Moreover, the NMC E4 has a lowlithium carbonate content of 0.104 wt % while the content in the NMC cE1is 0.196 wt %. Therefore, the Al/F layer reduces the amount of solublebase in the final product and stabilizes the surface against unwantedside reactions between the NMC surface and electrolytes, which resultsin enhanced cycling performance.

Comparative Example 4: Al Coated NMC Samples Prepared Using RoastedTransition Metal Source

An Al coated NMC sample NMC cE4 is obtained using the steps inComparative Example 1 and “Surface Coating Example 1” (as in Example 6).After blending with aluminum source and sintering, NMC powder issurrounding by Al layer on the surface.

Comparative Example 5: Al/F Coated NMC Samples Prepared Using RoastedTransition Metal Source

An Al coated NMC sample NMC cE5 is obtained from the Comparative Example2 and “Surface Coating Example 2” (as in Example 7). After blending withthe aluminum source and fluorine-containing polymer and subsequentsintering, NMC powder has an Al/F layer on the surface.

FIG. 9 shows the coin cell results of the NMC cE4 and NMC cE5 samples,where the square symbol is for NMC cE4 and the circle symbol is for NMCcE5. The coin cell test is conducted at the charge cutoff voltage of4.5V/Li metal and a 1C current definition of 160 mA/g. The cyclingstability of NMC cE5 is excellent, and from the Figure, it can beobserved that the NMC cE5 has an even better cycling stability than NMCcE2. The NMC product prepared by the pre-roasted transition metal sourcefurther shows a reduced content of soluble base in the final NMC productby Al/F layer and improved stability between the NMC surface and theelectrolyte. Accordingly, it shows an enhanced cycling performance.

Comparative Example 6: NMC Samples Prepared Using Various Air FlowConditions During the 1^(st) Sintering

An NMC powder with formula Li_(1.017)M′_(0.983)O₂ withM′=Ni_(0.4)(Ni_(0.5)Mn_(0.5))_(0.4)Co_(0.2) is prepared using the stepsin Comparative Example 1. In this example, in the rotary furnace for the1^(st) sintering, an air flow condition is set in the range from 0.5m³/kg to 2.0 m³/kg. In case of 0.5 m³/kg air flow, the sample islabelled NMC E6.1. When the air flow is 1.0 m³/kg and 2.0 m³/kg, thesamples are labelled as NMC E6.2 & NMC E6.3 respectively. FIG. 10 showsthe total base content in the final NMC products. As shown in thefigure, when the air flow during the first sintering is 0.5 m³/kg, thereis a large variation of total base amount, which can be attributed tothe low air flow that seems not enough to evacuate the produced CO₂ gascompletely, and results in larger amounts of lithium carbonate in thefinal product. When the air flow is 1.0 m³/kg and 2.0 m³/kg, it has abetter variation of total base. Therefore, in order to minimize theformation of soluble base, it is preferred to use an air flow of 1.0m³/kg or more.

FIG. 11 indicates the Li/M′ atomic ratio in various samples of theproduct after the 1^(st) sintering. In case of a slow air flow such as0.5 m³/kg, the incomplete removal of CO₂ gas during the preparationcauses an inhomogeneous composition. When the air flow is 1.0 m³/kg ormore, a better variation of Li/M′ atomic ratio is achieved. NMC cE6.3exhibits the best variation of Li/M′ atomic ratio after 1^(st)sintering. Therefore, to produce a high quality of NMC, an air flow of2.0 m³/kg is even better.

Example 5: Al/Sulfate Coated NMC Sample

An NMC powder with formula Li_(1.017)M′_(0.983)O₂ withM′=Ni_(0.45)(Ni_(0.50)Mn_(0.50))_(0.35)Co_(0.20) is prepared using thesteps of Example 1, except that a mixed nickel-manganese-cobaltoxyhydroxide (M′O_(0.39)(OH)_(1.61), whereM′=Ni_(0.625)Mn_(0.175)Co_(0.200)) is used as a precursor (M1) and thelithium deficient sintered precursor has a Li/M′ atomic ratio of 0.883.In the 1^(st) sintering step, the mixture of transition metal source andLiOH.H₂O is sintered at 820° C. in a rotary furnace for 2 hours(residence time) and 0.628 rpm of rotation speed, under dry air with aflow rate of 1.67 m³/kg. The crystalline size of the lithium deficientsintered precursor after the 1^(st) sintering is 26.2 nm. The 2^(nd)sintering is conducted at 845° C. for 10 hours under a dry airatmosphere in a tray based furnace. The dry air is continuously pumpedinto the equipment at a flow rate of 40 L/h. The sintered NMC product islabeled NMC E5.1.

The NMC product after the 2^(nd) sintering is blended with coatingsources using the steps of “Surface Coating Example 3”. First, the NMCpowder is blended with 1.2 wt % of sodium persulfate (Na₂S₂O₈) and 0.2wt % aluminum oxide (Al₂O₃). The blend is heated at 375° C. for 5 hoursunder air. The final product carries a coating comprising LiNaSO₄ andAl₂O₃, and is named NMC E5.2. Table 10 summarizes the electrochemicalperformance and soluble base content of NMC E5.1 and E5.2. The coin celltest is conducted at the charge cutoff voltage of 4.5V/Li metal and a 1Ccurrent definition of 160 mA/g.

TABLE 10 Performance of Example 5 DQ0.1 C 0.1 C QFad. 1 C QFad. Li₂CO₃Sample (mAh/g) (%/100) (%/100) (wt %) NMC E5.1 180.6 −1.04 3.41 0.301NMC E5.2 184.6 0.88 1.44 0.143

These examples have a high discharge capacity because of the highNi-excess of 0.45. The Al/Sulfur coating on the NMC sample reduces thesoluble base content and shows improved battery properties, such ashigher discharge capacity and cycling stability.

Other compositions of the crystalline precursor with a Ni-excess (z) of0.410 and 0.700 also have good electrochemical performance. Especially,the crystalline precursor having the range of ‘a’ from 0 to 0.053 in theformulaLi_(1-a)((Ni_(z)(Ni_(0.5)Mn_(0.5))_(y)Co_(x))_(1-k)A_(k))_(1+a)O₂ andthe Ni-excess range from 0.25 to 0.85 obtains the Li₂CO₃ content lessthan 0.4 wt %, which lead to low soluble base content of the final NMCpowder. Accordingly, the NMC powder has higher discharge capacity andlow capacity fading. Table 11 shows the summarized properties ofExamples, which are according to the present invention.

TABLE 11 Summary of Examples 1^(st) Intermediate product, firingLi_(1−a)((Ni_(z)(Ni_(0.5)Mn_(0.5))_(y)CO_(x))_(1−k)A_(k))_(1+a)O₂ NMCproduct, temper- Ni- CrystallineLi_(1−a′)((Ni_(z)(Ni_(0.5)Mn_(0.5))_(y)CO_(x))_(1−k)A_(k))_(1+a′)O₂ature excess Co A size L Li₂CO₃ Li₂CO₃ DQ0.1 C 1 C QFad. Sample Type (°C.) a z x k (nm) (wt %) Sample a′ (wt %) (mAh/g) (%/100)) Claim — —0-0.053 0.25-0.85 0.05-0.40 0-0.1 15-36 <0.4 — −0.10-0 — NMC E1p Poly*820 0.041 0.400 0.200 0.000 27.8 0.19 NMC E1 −0.017 0.206 179.5 5.4 NMCcE1p Poly* 820 0.061 0.400 0.200 0.000 35.4 0.14 NMC cE1 −0.017 0.196176.7 5.4 NMC cE2p Poly* 820 0.164 0.400 0.200 0.000 33.8 0.17 NMC cE2−0.017 0.245 179.0 8.7 NMC cE3p Poly* 720 0.161 0.400 0.200 0.000 31.10.25 NMC cE3 −0.017 0.256 176.5 7.4 NMC E2p Poly* 820 0.036 0.400 0.2000.000 26.2 0.21 NMC E2 −0.017 0.315 174.8 4.1 NMC E6p Mono** 770 0.0470.410 0.150 0.000 34.5 0.28 NMC E6 −0.021 0.099 176.8 9.0 NMC E7p Poly*750 0.005 0.700 0.100 0.000 33.1 0.29 NMC E7 −0.003 — 192.6 4.0 *Poly:Polycrystalline structure **Mono: Monolithic structure

The Li/M′ atomic ratio is equivalent to the ‘a’ value. In theintermediate product having the general formula: Li_(1-a)M′_(1+a)O₂, theLi/M′ ratio equals ‘(1−a)/(1+a). For example, if ‘a’ is 0.041 such asfor NMC E1p, then the Li/M′ ratio is ‘(1−0.041)/(1+0.041)=0.921’.Therefore, in the present invention, the intermediate product has aLi/M′ ratio from about 0.9+/−0.05 to 1.0+/−0.05 according to the claimedrange of ‘a’. As shown in Table 11, when ‘a’ of the intermediate productis in the range defined from 0 to 0.053, it leads to a dischargecapacity higher than or equal to 174.8 mAh/g and a 1C QFad. less than orequal to 5.4%, when converted into the NMC cathode material according toprocess described in the present invention. For example, NMC E1p has thedischarge capacity of 179.5 mAh/g and 1C QFad. of 5.4%.

The technical effects of NMC E12p and NMC E13p are further described asfollows.

Example 6: NMC Sample with a Ni-Excess of 0.41

A crystalline precursor, having the formulaLi_(0.953)(Ni_(0.41)(Ni_(0.5)Mn_(0.5))_(0.44)Co_(0.15))_(1.047)O₂ areprepared through a firing process which is a solid-state reactionbetween a lithium source and a transition metal-based source running asfollows:

1) Co-precipitation: a transition metal-based hydroxide precursorM′O_(0.27)(OH)_(1.73) (MTH1) with metal compositionM′=Ni_(0.45)(Ni_(0.5)Mn_(0.5))_(0.40)Co_(0.15) is prepared by aco-precipitation process in a large-scale continuous stirred tankreactor (CSTR) with mixed nickel-manganese-cobalt sulfates, sodiumhydroxide, and ammonia.

2) Heating: MTH1 is heated at 375° C. for 12 hours under dry airatmosphere so as to prepare a transition metal-based oxide (MTO1).

3) 1^(st) firing: MTO1 and LiOH as a lithium source are homogenouslymixed so as to prepare a 1^(st) mixture having a Li/M′ atomic ratio of0.91.

4) 1^(st) firing: the 1^(st) mixture is fired at 770° C. for 1 hourunder dry air atmosphere so as to prepare NMC E6p.

NMC E6p is according to the present invention.

To confirm the electrochemical performance of the NMC powder as apositive electrode active material, the monolithic NMC powder isobtained using the above crystalline precursor (NMC E6p) by thefollowing procedure:

1) 2^(nd) mixing: NMC E6p and LiOH.H₂O as a lithium source arehomogenously mixed so as to prepare a 2^(nd) mixture having a Li/M′atomic ratio of 1.043.

2) 2^(nd) firing: the 2^(nd) mixture is fired at 890° C. for 10 hoursunder dry air atmosphere so as to prepare a fired agglomerated powder.

3) Milling: the fired agglomerated powder is crushed. 50 g of thecrushed powder is put in a 250 mL vessel with 50 mL deionized water, 10mm ZrO₂ balls with a filling ratio of 25% of the volume of the vesseland 0.5 at % COSO₄ with respect to the total atomic ratio of Ni, Mn, andCo in NMC E12p. The vessel is rotated on a commercial ball millequipment for 15 hours with a milling speed of 20 cm/s.

4) Filtering and drying: the wet milled solid powder is separated fromwater by using a filter. The filtered wet milled NMC powder is dried at80° C. in an oven with dry air to obtain the monolithic NMC powder.

5) 3^(rd) mixing and 3^(rd) firing: the dried monolithic NMC powder ismixed with Al₂O₃, Co₃O₄, and LiOH. The amount of Co₃O₄ and LiOH is 2 at% and 3 at % with respect to the total atomic ratio of Ni, Mn, and Co inthe dried monolithic NMC powder, respectively. Al content is also 500ppm with respect to the total weight of the dried monolithic NMC powder.The 3^(rd) mixture is fired at 775° C. for 10 hours under dry airatmosphere so as to prepare a 2^(nd) agglomerated powder.

6) Post treatment: the 2^(nd) agglomerated powder is crushed,classified, and sieved so as to obtain NMC powder having a formulaLi_(1.024)M′_(0.976)O₂ (a=−0.024) withM′=Ni_(0.403)(Ni_(0.5)Mn_(0.5))_(0.430)Co_(0.167) and labelled NMC E6.

The crystallite size of NMC E6p is investigated as described in sectionD) XRD test. Li₂CO₃ contents of NMC E6p and NMC E6 are investigated asdescribed in section A) pH titration test. NMC E6 is also evaluate asdescribed in section E) Coin cell test. Wherein the coin cell test isconducted at the charge cutoff voltage of 4.5V/Li metal and a 1C currentdefinition of 160 mA/g. Analysis results are shown in Table 12 and Table13.

TABLE 12 Properties of Example 6 Li/M′ 1^(st) firing Crystallite atomictemperature size L Li₂CO₃ Example ID ratio (° C.) (nm) (wt %) NMC E6p0.91 770 34.5 0.279

TABLE 13 Performance of Example 12 Crystalline Li₂CO₃ DQ0.1 C 1 C QFad.NMC ID Type precursor (wt %) (mAh/g) (%/100)) NMC E6 Mono* EX3 0.099176.8 9.0 *Mono: Monolithic structure

The crystalline precursor (NMC E6p) has a crystallite size of 34.5 nmand a Li₂CO₃ content of 0.279 wt %. NMC E6, prepared using thecrystalline precursor according to the invention, has goodelectrochemical performance.

Example 7: NMC Sample with a Ni-Excess of 0.70

A crystalline precursor, having the formulaLi_(0.889)(Ni_(0.70)(Ni_(0.5)Mn_(0.5))_(0.20)Co_(0.10))_(1.111)O₂ areprepared through a firing process which is a solid-state reactionbetween a lithium source and a transition metal-based source running asfollows:

1) Co-precipitation: a transition metal-based hydroxide precursorM′O_(0.24)(OH)_(1.76) (MTH2) with metal compositionM′=Ni_(0.70)(Ni_(0.5)Mn_(0.5))_(0.20)Co_(0.12) is prepared by aco-precipitation process in a large-scale continuous stirred tankreactor (CSTR) with mixed nickel-manganese-cobalt sulfates, sodiumhydroxide, and ammonia.

2) Heating: MTH2 is heated at 400° C. for 11.75 hours under dry air andlabelled MTO2.

3) 1^(st) mixing: MTO2 and LiOH as a lithium source are homogenouslymixed so as to prepared a 1^(st) mixture having a Li/M′ atomic ratio of0.99.

4) 1^(st) firing: the 1^(st) mixture is fired at 730° C. for 2 hoursunder dry air atmosphere so as to prepare NMC E7p.

NMC E7p is according to the present invention.

To confirm the electrochemical performance of the NMC powder as apositive electrode active material, the polycrystalline NMC powder isobtained using the above crystalline precursor (NMC E7p) by thefollowing procedure:

1) 2^(nd) mixing: NMC E7p and LiOH as a lithium source are homogenouslymixed so as to prepare a 2^(nd) mixture having a Li/M′ atomic ratio of1.007.

2) 2^(nd) firing: the 2^(nd) mixture is fired at 830° C. for 12 hoursunder oxygen-containing atmosphere so as to prepare a fired agglomeratedpowder.

3) Post treatment: the fired agglomerated powder is crushed, classified,and sieved so as to obtain the NMC powder having a formulaLi_(1.003)M′_(0.997)O₂ (a=−0.003) withM′=Ni_(0.8)(Ni_(0.5)Mn_(0.5))_(0.2)Co_(0.1) and labelled NMC E7.1.

Surface treated NMC powder is prepared according to the followingprocedure. NMC E7.1 is mixed with an aluminum sulfate solution which isprepared using Al₂(SO₄)₃.16H₂O and deionized water. The amount of Al is1000 ppm with respect to the total weight of NMC E7.1. The mixture isfired at 375° C. for 8 hours under an oxygen atmosphere. The firedpowder is crushed, classified, and sieved so as to obtain NMC E7.2.

The crystallite size of NMC E7p is investigated as described in sectionD) XRD test. Li₂CO₃ contents of NMC E7p, NMC E7.1, and NMC E7.2 areinvestigated as described in section A) pH titration test. NMC E7.1 andNMC E7.2 are also evaluate as described in section E) Coin cell test.The coin cell test is conducted at the charge cutoff voltage of 4.3V/Limetal and a 1C current definition of 220 mA/g. The analysis results areshown in Table 14 and Table 15.

TABLE 14 Properties of Example 7 Li/M′ 1^(st) firing Crystallite atomicTemperature size L Li₂CO₃ Example ID ratio (° C.) (nm) (wt %) NMC E7p0.99 750 33.1 0.289

TABLE 15 Performance of Example 7 Li₂CO₃ DQ0.1 C 1 C QFad. NMC ID Type(wt %) (mAh/g) (%/100)) NMC E7.1 Poly* — 198.6 4.0 NMC E7.2 Poly* 0.145202.3 4.0 *Poly: Polycrystalline structure

The crystalline precursor (NMC E7p) has a crystallite size of 33.1 nmand a Li₂CO₃ content of 0.289 wt %. NMC E7.1 prepared using thecrystalline precursor according to the invention, has goodelectrochemical performance such as high discharge capacity. The surfacetreated NMC powder, NMC E7.2, has a higher discharge capacity.

The invention is further covered by the following clauses:

1. A crystalline precursor compound for manufacturing a lithiumtransition metal based oxide powder usable as an active positiveelectrode material in lithium-ion batteries, the precursor having ageneral formulaLi_(1-a)((Ni_(z)(Ni_(0.5)Mn_(0.5))_(y)Co_(x))_(1-k)A_(k))_(1+a)O₂,wherein A comprises at least one element of the group consisting of: Mg,Al, Ca, Si, B, W, Zr, Ti, Nb, Ba, and Sr, with 0.05≤x≤0.40, 0.25≤z≤0.85,x+y+z=1, 0≤k≤0.10, and 0≤a≤0.053, wherein said crystalline precursorpowder has a crystalline size L, expressed in nm, with 15≤L≤36.

2. The crystalline precursor compound of clauses 1, having a Li₂CO₃content of inferior to 0.4 wt %.

3. The crystalline precursor compound of clauses 1, wherein0.03≤a≤0.053.

4. The crystalline precursor compound of clauses 1, wherein 0.35≤z≤0.50

5. The crystalline precursor compound of clauses 1, wherein theprecursor has an integrated intensity ratio I003/I104<1, wherein I003and I104 are the peak intensities of the Bragg peaks (003) and (104) ofthe XRD pattern of the crystalline precursor compound.

6. The crystalline precursor compound of clauses 1, wherein theprecursor has an integrated intensity ratio I003/I104<0.9.

7. The crystalline precursor compound of clauses 1, wherein theprecursor has a ratio R of the intensities of the combined Bragg peak(006, 102) and the Bragg peak (101) with R=((I006+I102)/I101) and0.5<R<1.16.

8. The crystalline precursor compound of clauses 1, wherein theprecursor has a crystalline size L expressed in nm, with 25≤L≤36.

9. A method for preparing a positive electrode material having thegeneral formula Li_(1-a′)M′_(1+a′)O₂, withM′=(Ni_(z)(Ni_(0.5)Mn_(0.5))_(y)Co_(x))_(1-k)A_(k), wherein x+y+z=1,0.05≤x≤0.40, 0.25≤z≤0.85, A is a dopant, 0≤k≤0.1, and −0.10≤a′≤0, themethod comprising the steps of:

-   -   providing a M′-based precursor prepared from the        co-precipitation of metal salts with a base;    -   mixing the M′-based precursor with either one of LiOH, Li₂O and        LiOH.H₂O, thereby obtaining a first mixture, whereby the Li to        transition metal ratio in the first mixture is between 0.90 and        1.00,    -   sintering the first mixture in an oxidizing atmosphere in a        rotary kiln at a temperature between 650 and 850° C., for a time        between ⅓ hour and 3 hours, thereby obtaining a lithium        deficient precursor powder according to any one of claims 1 to        7,    -   mixing the lithium deficient precursor powder with either one of        LiOH, Li₂O and LiOH.H₂O, thereby obtaining a second mixture, and    -   sintering the second mixture in an oxidizing atmosphere at a        temperature between 800 and 1000° C., for a time between 6 hours        and 36 hours.

10. A method for preparing a positive electrode material comprising acore material having the general formula Li_(1-a′)M′_(1+a′)O₂, withM′=(Ni_(z)(Ni_(0.5)Mn_(0.5))_(y)Co_(x))_(1-k)A_(k), wherein x+y+z=1,0.05≤x≤0.40, 0.25≤z≤0.85, A is a dopant, 0≤k≤0.1, and −0.10≤a′≤0, and acoating comprising a metal M″, the method comprising the steps of claim8 for obtaining the core material, and additionally the steps of either:

A1) providing a third mixture comprising the core material and acompound comprising M″, and

A2) heating the third mixture to a sintering temperature between 600° C.and 800° C.; or

B1) providing a fourth mixture comprising the core material, afluorine-containing polymer and a compound comprising M″, and

B2) heating the fourth mixture to a sintering temperature between 250and 500° C., or

C1) providing a fifth mixture comprising the core material, an inorganicoxidizing chemical compound, and a chemical that is a Li-acceptor, and

C2) heating the fifth mixture at a temperature between 300 and 800° C.in an oxygen comprising atmosphere.

11. The method according to clauses 10, wherein the compound comprisingM″ in either one of steps A1) and B1) is either one or more of an oxide,a sulfate, a hydroxide and a carbonate, and M″ is either one or more ofthe elements Al, Ca, Ti, Mg, W, Zr, B, Nb and Si.

12. The method according to clauses 11, wherein the compound comprisingM″ is a nanometric alumina powder having a D50 of inferior to 100 nm anda surface area of at least 50 m²/g.

13. The method according to clauses 10, wherein the fluorine-containingpolymer in step B1) is either one of a PVDF homopolymer, a PVDFcopolymer, a PVDF-HFP polymer (hexa-fluoro propylene) and a PTFEpolymer, and wherein the amount of fluorine-containing polymer in thefourth mixture is between 0.1 wt % and 2 wt %.

14. The method according to clauses 9, wherein through the rotary kilnan air flow is applied between 0.5 m³/kg and 3.5 m³/kg.

15. The method according to clauses 9, wherein the step of sintering thesecond mixture is performed in a tray conveyor furnace wherein each traycarries at least 5 kg of mixture.

16. The method according to clauses 9, wherein between the step ofproviding a M′-based precursor and the step of mixing the M′-basedprecursor with either one of LiOH, Li₂O and LiOH.H₂O the M′-basedprecursor is subjected to a roasting step at a temperature above 200° C.in a protective atmosphere, such as under N₂.

17. The method according to clauses 16, wherein the transition metals inthe M′-based precursor have a mean oxidation state of superior to 2.5and wherein the precursor has a content of H₂O of inferior to 15 wt %.

18. The method according to clauses 16, wherein the transition metals inthe M′-based precursor have a mean oxidation state of superior to 2.7and wherein the precursor has a content of H₂O of inferior to 5 wt %.

19. The method according to clauses 10 comprising steps C1) and C2),wherein M″=Li, and in step C1) the inorganic oxidizing chemical compoundis NaHSO₅, or either one of a chloride, a chlorate, a perchlorate and ahypochloride of either one of potassium, sodium, lithium, magnesium andcalcium, and the Li-acceptor chemical is either one of AlPO₄, Li₃AlF₆and AlF₃.

20. The method according to clauses 10 comprising steps C1) and C2),wherein M″=Li, and in step C1) both the inorganic oxidizing chemicalcompound and the Li-acceptor chemical are the same compound, beingeither one of Li₂S₂O₈, H₂S₂O₈ and Na₂S₂O₈.

21. The method according to clauses 10 comprising steps C1) and C2),wherein in step C1) a nanosized Al₂O₃ powder is provided as a furtherLi-acceptor chemical.

1. A crystalline precursor compound for manufacturing a lithiumtransition metal based oxide powder usable as an active positiveelectrode material in lithium-ion batteries, the precursor having ageneral formulaLi_(1-a)((Ni_(z)(Ni_(0.5)Mn_(0.5))_(y)Co_(x))_(1-k)A_(k))_(1+a)O₂,wherein A comprises at least one element of the group consisting of: Mg,Al, Ca, Si, B, W, Zr, Ti, Nb, Ba, and Sr, with 0.05≤x≤0.40, 0.25≤z≤0.85,x+y+z=1, 0≤k≤0.10, and 0≤a≤0.053, wherein said crystalline precursorpowder has a crystalline size L, expressed in nm, with 15≤L≤36.
 2. Thecrystalline precursor compound of claim 1, having a Li₂CO₃ content ofinferior to 0.4 wt %.
 3. The crystalline precursor compound of claim 1,wherein 0.03≤a≤0.053.
 4. The crystalline precursor compound of claim 1,wherein 0.35≤z≤0.50
 5. The crystalline precursor compound of claim 1,wherein the precursor has an integrated intensity ratio I003/I104<1,wherein I003 and I104 are the peak intensities of the Bragg peaks (003)and (104) of the XRD pattern of the crystalline precursor compound. 6.The crystalline precursor compound of claim 1, wherein the precursor hasan integrated intensity ratio I003/I104<0.9.
 7. The crystallineprecursor compound of claim 1, wherein the precursor has a ratio R ofthe intensities of the combined Bragg peak (006, 102) and the Bragg peak(101) with R=((I006+I102)/I101) and 0.5<R<1.16.
 8. The crystallineprecursor compound of claim 1, wherein the precursor has a crystallinesize L expressed in nm, with 25≤L≤36.